With an efficient atom economy, low activation energy, and valuable applications for fuel cells and hydrogen storage, formic acid (FA) is a useful fuel product to convert CO2 and reduce emissions. Although metal catalysts are typically used for this conversion, unwanted side reactions remain a concern, particularly when products are attempted to be recovered long-term. In this study, an enzymatic catalyst is used to enable the selective conversion of CO2 to FA, as a formate ion. A dual-cell flow reactor system is used to first reduce a charge mediator electrochemically (reduction cell), which then activates a catalyst to selectively convert CO2 to formate (production cell). This approach minimizes enzyme degradation by avoiding direct contact with increased voltages and improves the quantity of formate produced. The system produced 25 mM of formate and reached over 50% Coulombic efficiency. The larger volume of this dual-cell system increases the quantity of formate produced beyond that of a batch cell. Additional design configurations are employed, including a pH control pump to maintain catalyst activity and a packed bed reactor to improve contact of the charge carrier with the catalyst. Both configurations retained higher production and efficiency long-term (∼168 h). The results highlight the challenges of developing a system where many parameters play a role in optimizing performance. Nevertheless, the ability of the system to produce formate from CO2 demonstrates the potential to improve upon this configuration for a variety of electrochemical CO2 conversion applications.
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